CN111097525A - Solid acid catalyst for olefin epoxidation reaction and preparation method and application - Google Patents
Solid acid catalyst for olefin epoxidation reaction and preparation method and application Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 89
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 25
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 238000006735 epoxidation reaction Methods 0.000 title claims abstract description 20
- 239000011973 solid acid Substances 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000000843 powder Substances 0.000 claims abstract description 84
- 239000011964 heteropoly acid Substances 0.000 claims abstract description 81
- 229910052809 inorganic oxide Inorganic materials 0.000 claims abstract description 44
- 238000006884 silylation reaction Methods 0.000 claims abstract description 41
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 17
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 16
- BQQUFAMSJAKLNB-UHFFFAOYSA-N dicyclopentadiene diepoxide Chemical compound C12C(C3OC33)CC3C2CC2C1O2 BQQUFAMSJAKLNB-UHFFFAOYSA-N 0.000 claims abstract description 16
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims abstract description 14
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 10
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 5
- 230000003647 oxidation Effects 0.000 claims abstract description 4
- 239000002904 solvent Substances 0.000 claims description 44
- 239000007787 solid Substances 0.000 claims description 38
- 238000005406 washing Methods 0.000 claims description 33
- 238000003756 stirring Methods 0.000 claims description 26
- 238000002156 mixing Methods 0.000 claims description 22
- 125000000864 peroxy group Chemical group O(O*)* 0.000 claims description 21
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 18
- 238000005303 weighing Methods 0.000 claims description 18
- 238000001914 filtration Methods 0.000 claims description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- 239000004593 Epoxy Substances 0.000 claims description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 230000007935 neutral effect Effects 0.000 claims description 8
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052681 coesite Inorganic materials 0.000 claims description 6
- 229910052593 corundum Inorganic materials 0.000 claims description 6
- 229910052906 cristobalite Inorganic materials 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 229910052682 stishovite Inorganic materials 0.000 claims description 6
- 229910052905 tridymite Inorganic materials 0.000 claims description 6
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 6
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims description 4
- 230000004048 modification Effects 0.000 claims description 4
- 238000012986 modification Methods 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 claims description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 claims description 2
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 claims description 2
- 150000002978 peroxides Chemical class 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000004437 phosphorous atom Chemical group 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000005342 ion exchange Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 34
- 239000002994 raw material Substances 0.000 description 18
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 12
- 230000001590 oxidative effect Effects 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 9
- 239000007800 oxidant agent Substances 0.000 description 8
- 239000003822 epoxy resin Substances 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- -1 benzoyl peroxide dicyclopentadiene Chemical compound 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 150000002118 epoxides Chemical class 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000003944 halohydrins Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000005340 laminated glass Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- 238000011020 pilot scale process Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/182—Phosphorus; Compounds thereof with silicon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
- B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
- B01J27/1802—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates
- B01J27/1806—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates with alkaline or alkaline earth metals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
- C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
- C07D493/08—Bridged systems
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Epoxy Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
本发明提供了一种用于烯烃环氧化反应固体酸催化剂和制备方法及应用。该催化剂采用季铵盐接枝改性处理的纳米无机氧化物为载体，活性组分为杂多酸或过氧杂多酸。其制备方法的步骤包括：采用含季铵盐的硅烷基化试剂接枝改性处理无机氧化物，得到催化剂载体；通过离子交换，将杂多酸或过氧杂多酸吸附在氧化物载体表面，经水洗、烘干得到催化剂原粉；用硅溶胶或铝溶胶与催化剂原粉混合、搅拌、造粒、干燥处理，得到颗粒状催化剂。本发明制备的催化剂，催化性能稳定，反应活性高，绿色环保，适用于烯烃环氧化反应，尤其适用于双环戊二烯氧化制备二氧化双环戊二烯领反应，具有良好的工业应用前景。The invention provides a solid acid catalyst for olefin epoxidation reaction, a preparation method and application. The catalyst adopts nanometer inorganic oxides grafted and modified by quaternary ammonium salt as carrier, and the active component is heteropolyacid or peroxoheteropolyacid. The preparation method includes the following steps: adopting a quaternary ammonium salt-containing silylation reagent to graft and modify an inorganic oxide to obtain a catalyst carrier; and adsorbing a heteropolyacid or a peroxoheteropolyacid on the surface of the oxide carrier through ion exchange , washed with water and dried to obtain the original catalyst powder; mixed, stirred, granulated and dried with silica sol or aluminum sol and the original catalyst powder to obtain a granular catalyst. The catalyst prepared by the invention has stable catalytic performance, high reaction activity and environmental protection, is suitable for olefin epoxidation reaction, especially suitable for the reaction of dicyclopentadiene dioxide prepared by oxidation of dicyclopentadiene, and has good industrial application prospect.
Description
Technical Field
The invention belongs to the field of chemical industry, and particularly relates to a solid acid catalyst for olefin epoxidation reaction, and a preparation method and application thereof.
Background
Because of the excellent performance of dicyclopentadiene dioxide, dicyclopentadiene dioxide is widely used in the key technical fields of military industry, aviation, aerospace and the like abroad. Compared with bisphenol A series epoxy resin, dicyclopentadiene dioxide is expected to become a new generation of epoxy resin product with important influence in high-end fields of electric appliances and the like, so that the improvement and improvement of the synthesis process of dicyclopentadiene dioxide increasingly becomes the research focus in the field.
Dicyclopentadiene dioxide is usually industrially prepared from dicyclopentadiene (DCPD) through epoxidation reaction by methods such as a peracetic acid method, a halohydrin method, a hydroperoxide catalytic epoxidation method and the like, but the three methods all have the defects at present, such as complex reaction process, serious equipment corrosion, easy generation of by-products by acidic ring opening of epoxide, high discharge of three wastes and the like. Dicyclopentadiene dioxide was first prepared by h.wieland et al in 1925 from benzoyl peroxide dicyclopentadiene oxide. The production of small scale is carried out in early foreign countries by using relatively cheap peracetic acid as an oxidant. In the sixties of the last century, the Shanghai research institute for synthetic resins began to synthesize dicyclopentadiene dioxide products. In the seventies of the last century, dicyclopentadiene dioxide industrial products, namely the brand Hy-101 epoxy resin, were also tried out by the Tianjin chemical research institute and the Tianjin Dong chemical plant by a prefabricated aqueous peracetic acid method, and research was conducted on the application of the resin in the fields of castable, glass laminate, high temperature resistant adhesive, B-stage resin and the like. 40t/a pilot-scale technical development of synthesizing dicyclopentadiene dioxide by an acetaldehyde oxidation method is completed in 1984 by Shanghai Shi Ming Dynasty chemical Co. Because of adopting the production process of the peroxyacetic acid method, the production yield is low, the cost is high, the danger of the production process is high, the equipment corrosion is serious and the like, and the development and the application of the dicyclopentadiene dioxide product are limited. Therefore, the Shanghai resin factory, Tianjin Dong chemical factory and other factories which originally research and develop dicyclopentadiene dioxide in China only have small-batch production due to the adoption of the peracid method, and the production cost is higher. Dicyclopentadiene dioxide produced by the industrial and industrial company Limited of Changde in Yueyang in Hunan by peroxyacetic acid oxidation method is CDR-0122, and the productivity is less than 100 tons.
The heteropoly acid catalyst is paid much attention in the research field of olefin epoxidation reaction at present, the quaternary ammonium salt type phosphotungstic heteropoly acid compound catalyst system disclosed by Venturi and Ishii has the conversion rate of more than 95 percent when being used for most olefin epoxidation reactions such as 1-octene, cyclohexene, styrene and the like, and the epoxide selectivity is 80 percent, but the defects of difficult catalyst recovery, less repeated use frequency and the like generally exist. The heteropoly acid is loaded on the surface of the silicon dioxide by an immersion method and a sol-gel method, although the problem of catalyst recovery can be solved, the solution of the heteropoly acid falls off from the surface of a catalyst carrier in the reaction process, the service life of the catalyst is short, the catalyst is generally reused for 5-6 times, the activity of the catalyst is obviously reduced, and the heteropoly acid can not be used for an industrial generation device.
Disclosure of Invention
In view of the problems in the prior art, the invention provides a solid acid catalyst for olefin epoxidation reaction, and a preparation method and application thereof. The catalyst provided by the invention takes inorganic oxide which is subjected to graft modification treatment by a silylation reagent containing quaternary ammonium salt as a carrier, and heteropoly acid or peroxy heteropoly acid which is taken as an active component of the catalyst is firmly adsorbed on the surface of the carrier by ionic bonds, so that the active component of the catalyst has the advantages of large specific surface area, high catalytic activity, stable performance, long service life and the like, can be used for a fixed bed reactor, is convenient to separate products from the catalyst, and is easy to use in an industrial production device.
The invention provides a solid acid catalyst for olefin epoxidation reaction, which adopts inorganic oxide grafted and modified by a silylation reagent containing quaternary ammonium salt as a carrier and adopts heteropoly acid or peroxy heteropoly acid as an active component, wherein the inorganic oxide is nano MgO or SiO2、Al2O3Or any combination thereof.
The invention also provides a preparation method of the solid acid catalyst for olefin epoxidation, which comprises the following steps:
the inorganic oxide is subjected to graft modification treatment by using a silylation reagent containing quaternary ammonium salt to obtain a catalyst carrier, and specifically:
(1) weighing a certain amount of inorganic oxide powder, a silylation reagent and a solvent, putting into a reactor, mixing and stirring to react, wherein the reaction temperature is in the range of 30-120 ℃, and the reaction time is in the range of 8-30 hours;
wherein: the inorganic oxide powder is nano MgO or SiO2、Al2O3The silylation reagent is a silylation reagent containing quaternary ammonium salt groups, and the silylation reagent has any one of the following two chemical formulas:
RmSi(OR)3-m(CH2)nN+R1R2R3X-(1)
RmSiX3-m(CH2)nN+R1R2R3X-(2)
wherein N, O, Si in chemical formulas (1) and (2) respectively represent nitrogen, oxygen and silicon elements; x represents halogen, and any one of F, Cl, Br and I elements is selected, preferably Cl; m represents the number of alkyl groups bonded to the silicon atom, and is an integer of 0 to 2; n represents the number of methylene groups connected between silicon and phosphorus atoms, and is an integer of 1-18, preferably 1-3; r, R1、R2、R3The alkyl group is selected from alkyl groups with 1-18 carbon atoms, phenyl groups or benzyl groups, the alkyl group is preferably any one of methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, heptyl, octyl, dodecyl, tetradecyl, hexadecyl and octadecyl, and is preferably methyl, ethyl, propyl or isopropyl;
the solvent is one or any combination of benzene, toluene, petroleum ether, dichloroethane, acetonitrile, tetrahydrofuran, 1, 2-epoxy hexacyclic ring and dichloroethane; the molar ratio of the inorganic oxide powder to the silylation agent is 25: 1-740: 1, and the mass ratio of the solvent to the inorganic oxide powder is 5: 1-2: 1;
(2) filtering the product in the step (1), separating solid powder from the solution, washing the separated solid powder with the solvent in the step (1), wherein the mass ratio of the solvent for washing to the inorganic oxide powder in the step (1) is 5: 1-2: 1, removing unreacted silylation reagent in the solid powder, and drying the solid powder;
(II) adsorbing heteropoly acid or peroxy heteropoly acid on the surface of an oxide carrier through ion exchange, washing with water, and drying to obtain catalyst raw powder, specifically:
(3) preparing a heteropoly acid solution: weighing a certain amount of heteropoly acid and dissolving the heteropoly acid in a solvent, wherein the concentration of the heteropoly acid is 0.01-0.20 g/ml, and the solvent is any one or a mixture of more of pure water, methanol, ethanol, acetone, chloromethane, tetrahydrofuran and 1, 4-dioxane; or, preparing a peroxy heteropoly acid solution: weighing a certain amount of heteropoly acid solid, slowly adding the heteropoly acid solid into hydrogen peroxide solution with the mass concentration of 30-70 percent, and mixing heteropoly acid and H2O2The mass ratio is 1: 1-1: 3, and stirring is carried out for 2-5 hours at the temperature of 20-30 ℃ to obtain a peroxy heteropoly acid solution;
wherein the molar ratio of the heteropoly acid or the peroxy heteropoly acid to the silylation reagent is 1: 1-1: 3;
(4) adding the solid powder obtained in the step (2) into the heteropoly acid or heteropoly acid peroxide solution prepared in the step (3), controlling the temperature at 30-80 ℃, stirring for 20-30 h, filtering, separating to obtain a product, washing with deionized water until the washing water is neutral, and baking in an oven at 40-120 ℃ for 10-40 h to obtain raw catalyst powder;
(III) mixing silica sol or alumina sol with raw catalyst powder, stirring, granulating and drying to obtain a granular catalyst, specifically:
(5) mixing the catalyst raw powder obtained in the step (4) with silica sol or aluminum sol, wherein the mass ratio of the catalyst raw powder to the silica sol or the aluminum sol is 4: 1-1: 1, the mass percentage concentration of the silica sol or the aluminum sol is 20-30%, stirring, granulating, and baking at 70-120 ℃ for 10-30 hours to obtain a granular catalyst finished product.
The invention also provides an application of the solid acid catalyst for olefin epoxidation reaction, the catalyst is applied to olefin epoxidation reaction, and preferably, the catalyst is applied to reaction for preparing dicyclopentadiene dioxide by oxidizing dicyclopentadiene.
The key technical point of the invention is that quaternary ammonium salt ion groups are introduced on the surface of inorganic oxide through chemical reaction, so that heteropoly acid is highly dispersed on the surface of the catalyst, and the activity of the catalyst is very high; the quaternary ammonium salt group is connected with the surface of the inorganic oxide by a silica covalent bond, and the quaternary ammonium salt cation is combined with the heteropoly acid anion by an ionic bond, so that the problem of heteropoly acid loss is effectively solved, and the activity of the catalyst is stable.
The catalyst prepared by the method takes hydrogen peroxide as an oxidant to oxidize dicyclopentadiene and other olefins into epoxy compounds, and the product yield is more than 96%.
The invention has the advantages that: (1) the catalyst provided by the invention has stable catalytic performance and high reaction activity; (2) the reaction products are mainly epoxy compounds and water, and have the advantages of environmental protection and the like; (3) the product and the catalyst are simple and convenient to separate, and can be used for fixed bed reaction; (4) the method is suitable for olefin epoxidation reaction, and is particularly suitable for the field of preparing dicyclopentadiene dioxide by oxidizing dicyclopentadiene; (5) compared with the existing peroxyacetic acid oxidation reaction process, the method has more competitiveness and good industrial application prospect.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that it would be apparent to those skilled in the art that several modifications and improvements can be made without departing from the inventive concept. All falling within the scope of the present invention. In examples 1 to 6, the molecular structural formulas of the silylation agents used for modifying the nano inorganic oxide are shown in (1) to (6):
example 1
Selecting nano MgO as an inorganic oxide carrier, selecting a silylation reagent with a molecular structural formula (1) and benzene as a solvent, and preparing the catalyst according to the following steps:
(1) weighing the raw materials according to the molar ratio of the inorganic oxide powder to the silylation reagent of 100:1 and the mass ratio of the solvent to the inorganic oxide powder of 5:1, putting the raw materials into a reactor, mixing and stirring the raw materials to react at the reaction temperature of 30 ℃ for 8 hours;
(2) filtering the product in the step (1), separating solid powder from the solution, washing the separated solid powder with the solvent in the step (1), wherein the mass ratio of the solvent for each washing to the inorganic oxide powder in the step (1) is 5:1, removing unreacted silylation reagent in the solution, and drying the solution;
(3) preparing a heteropoly acid solution: weighing a certain amount of dodecaphosphotungstic heteropoly acid and dissolving in a solvent, wherein the solvent is pure water; the concentration of the heteropoly acid is 0.01 g/ml; wherein the molar ratio of heteropolyacid to silylating agent is 1: 1;
(4) adding the solid powder obtained in the step (2) into the heteropoly acid solution prepared in the step (3), controlling the temperature at 30 ℃, stirring for 20h, filtering, separating to obtain a product, washing with deionized water until the washing water is neutral, and baking in a 40 ℃ oven for 10h to obtain raw catalyst powder;
(5) and (3) mixing the catalyst raw powder obtained in the step (4) with silica sol, wherein the mass ratio of the catalyst raw powder to the silica sol is 4:1, the mass percentage concentration of the silica sol is 20%, stirring, granulating, and baking at 70 ℃ for 10 hours to obtain a granular catalyst finished product.
The prepared catalyst is used for oxidizing olefin such as dicyclopentadiene and the like into epoxy compounds by using hydrogen peroxide as an oxidizing agent, and the product yield is 96.9%.
Example 2
Selecting nano MgO as an inorganic oxide carrier, selecting a silylation reagent with a molecular structural formula (2) and toluene as a solvent, and preparing the catalyst according to the following steps:
(1) weighing the raw materials according to the molar ratio of the inorganic oxide powder to the silylation reagent of 25:1 and the mass ratio of the solvent to the inorganic oxide powder of 2:1, putting the raw materials into a reactor, mixing and stirring the raw materials to react at the reaction temperature of 120 ℃ for 6 hours;
(2) filtering the product in the step (1), separating solid powder from the solution, washing the separated solid powder with the solvent in the step (1), wherein the mass ratio of the solvent for each washing to the inorganic oxide powder in the step (1) is 2:1, removing unreacted silylation reagent in the solution, and drying the solution;
(3) preparing a peroxy heteropoly acid solution: weighing a certain amount of dodecaphosphotungstic heteropoly acid solid, slowly adding the dodecaphosphotungstic heteropoly acid solid into a hydrogen peroxide solution with the mass concentration of 30 percent, and mixing heteropoly acid and H2O2The mass ratio is 1:1, and the mixture is stirred for 2 hours at the temperature of 20 ℃ to obtain a peroxy heteropoly acid solution; wherein the molar ratio of the peroxy heteropoly acid to the silylation reagent is 1: 1;
(4) adding the solid powder obtained in the step (2) into the peroxy heteropoly acid solution prepared in the step (3), controlling the temperature at 80 ℃, stirring for 30h, filtering, separating to obtain a product, washing with deionized water until the washing water is neutral, and baking in a 120 ℃ oven for 40h to obtain raw catalyst powder;
(5) and (3) mixing the catalyst raw powder obtained in the step (4) with aluminum sol, wherein the mass ratio of the catalyst raw powder to the aluminum sol is 1:1, the mass percentage concentration of the aluminum sol is 30%, stirring, granulating, and baking at 120 ℃ for 30 hours to obtain a granular catalyst finished product.
The prepared catalyst is used for oxidizing olefin such as dicyclopentadiene and the like into epoxy compounds by using hydrogen peroxide as an oxidizing agent, and the product yield is 97.3%.
Example 3
Selecting nano SiO2As inorganic oxide carrier, silylation reagent with molecular structural formula (3) and petroleum ether as solvent are selectedThe catalyst was prepared as follows:
(1) weighing the raw materials according to the molar ratio of 740:1 of the inorganic oxide powder to the silylation reagent and the mass ratio of 4:1 of the solvent to the inorganic oxide powder, putting the raw materials into a reactor, mixing and stirring the raw materials to react at the reaction temperature of 50 ℃ for 10 hours;
(2) filtering the product in the step (1), separating solid powder from the solution, washing the separated solid powder with the solvent in the step (1), wherein the mass ratio of the solvent for each washing to the inorganic oxide powder in the step (1) is 4:1, removing unreacted silylation reagent in the solution, and drying the solution;
(3) preparing a heteropoly acid solution: weighing a certain amount of dodecasilicotungstic heteropoly acid and dissolving in a solvent, wherein the solvent is methanol; the concentration of the heteropoly acid is 0.02 g/ml; wherein the molar ratio of the heteropoly acid to the silylation reagent is 1: 3;
(4) adding the solid powder obtained in the step (2) into the heteropoly acid solution prepared in the step (3), controlling the temperature at 40 ℃, stirring for 25h, filtering, separating to obtain a product, washing with deionized water until the washing water is neutral, and baking in a 60 ℃ oven for 20h to obtain raw catalyst powder;
(5) and (3) mixing the catalyst raw powder obtained in the step (4) with silica sol, wherein the mass ratio of the catalyst raw powder to the silica sol is 3:1, the mass percentage concentration of the silica sol is 25%, stirring, granulating, and baking at 80 ℃ for 15 hours to obtain a granular catalyst finished product.
The prepared catalyst is used for oxidizing olefin such as dicyclopentadiene and the like into epoxy compounds by using hydrogen peroxide as an oxidizing agent, and the product yield is 98.1%.
Example 4
Selecting nano SiO2The catalyst is prepared by using a silylation reagent with a molecular structural formula (4) and acetonitrile as a solvent as an inorganic oxide carrier according to the following steps:
(1) weighing the raw materials according to the molar ratio of the inorganic oxide powder to the silylation reagent of 200:1 and the mass ratio of the solvent to the inorganic oxide powder of 3:1, putting the raw materials into a reactor, mixing and stirring the raw materials to react at the reaction temperature of 80 ℃ for 15 hours;
(2) filtering the product in the step (1), separating solid powder from the solution, washing the separated solid powder with the solvent in the step (1), wherein the mass ratio of the solvent for each washing to the inorganic oxide powder in the step (1) is 3:1, removing unreacted silylation reagent in the solution, and drying the solution;
(3) preparing a peroxy heteropoly acid solution: weighing a certain amount of dodecaphosphomolybdic heteropoly acid solid, slowly adding the dodecaphosphomolybdic heteropoly acid solid into hydrogen peroxide solution with the mass concentration of 70 percent, and mixing heteropoly acid and H2O2The mass ratio is 1:3, and the mixture is stirred for 5 hours at the temperature of 30 ℃ to obtain a peroxy heteropoly acid solution; wherein the molar ratio of the peroxy heteropoly acid to the silylation reagent is 1: 3;
(4) adding the solid powder obtained in the step (2) into the peroxy heteropoly acid solution prepared in the step (3), controlling the temperature at 60 ℃, stirring for 20h, filtering, separating to obtain a product, washing with deionized water until the washing water is neutral, and baking in an oven at 80 ℃ for 25h to obtain raw catalyst powder;
(5) and (3) mixing the catalyst raw powder obtained in the step (4) with aluminum sol, wherein the mass ratio of the catalyst raw powder to the aluminum sol is 2:1, the mass percentage concentration of the aluminum sol is 30%, stirring, granulating, and baking at 90 ℃ for 25 hours to obtain a granular catalyst finished product.
The prepared catalyst is used for oxidizing olefin such as dicyclopentadiene and the like into epoxy compounds by using hydrogen peroxide as an oxidizing agent, and the product yield is 98.5%.
Example 5
Selecting nano Al2O3The catalyst is prepared by using a silylation reagent with a molecular structural formula (5) as an inorganic oxide carrier and tetrahydrofuran as a solvent according to the following steps:
(1) weighing the raw materials according to the molar ratio of the inorganic oxide powder to the silylation reagent of 350:1 and the mass ratio of the solvent to the inorganic oxide powder of 3:1, putting the raw materials into a reactor, mixing and stirring the raw materials to react at the reaction temperature of 100 ℃ for 20 hours;
(2) filtering the product in the step (1), separating solid powder from the solution, washing the separated solid powder with the solvent in the step (1), wherein the mass ratio of the solvent for each washing to the inorganic oxide powder in the step (1) is 3:1, removing unreacted silylation reagent in the solution, and drying the solution;
(3) preparing a heteropoly acid solution: weighing a certain amount of dodecasilicomolybdic heteropoly acid and dissolving in a solvent, wherein the solvent is ethanol; the concentration of the heteropoly acid is 0.02 g/ml; wherein the molar ratio of the heteropoly acid to the silylation reagent is 1: 2;
(4) adding the solid powder obtained in the step (2) into the heteropoly acid solution prepared in the step (3), controlling the temperature at 70 ℃, stirring for 25h, filtering, separating to obtain a product, washing with deionized water until the washing water is neutral, and baking in a 100 ℃ oven for 30h to obtain raw catalyst powder;
(5) and (3) mixing the catalyst raw powder obtained in the step (4) with silica sol, wherein the mass ratio of the catalyst raw powder to the silica sol is 4:1, the mass percentage concentration of the silica sol is 30%, stirring, granulating, and baking at 110 ℃ for 15 hours to obtain a granular catalyst finished product.
The prepared catalyst is used for oxidizing olefin such as dicyclopentadiene and the like into epoxy compounds by using hydrogen peroxide as an oxidizing agent, and the product yield is 97.5%.
Example 6
Selecting nano Al2O3The catalyst was prepared as an inorganic oxide support using a silylating agent having the molecular formula (6) and dichloroethane as a solvent, according to the following procedure:
(1) weighing the raw materials according to the molar ratio of the inorganic oxide powder to the silylation reagent of 500:1 and the mass ratio of the solvent to the inorganic oxide powder of 4:1, putting the raw materials into a reactor, mixing and stirring the raw materials for reaction at the reaction temperature of 110 ℃ for 25 hours;
(2) filtering the product in the step (1), separating solid powder from the solution, washing the separated solid powder with the solvent in the step (1), wherein the mass ratio of the solvent for each washing to the inorganic oxide powder in the step (1) is 4:1, removing unreacted silylation reagent in the solution, and drying the solution;
(3) preparation ofPeroxy heteropoly acid solution: weighing a certain amount of dodecasilicomolybdic heteropoly acid solid, slowly adding the dodecasilicomolybdic heteropoly acid solid into hydrogen peroxide solution with the mass concentration of 50 percent, and mixing heteropoly acid and H2O2The mass ratio is 1:2, and the mixture is stirred for 4 hours at the temperature of 25 ℃ to obtain a peroxy heteropoly acid solution; wherein the molar ratio of the peroxy heteropoly acid to the silylation reagent is 1: 2;
(4) adding the solid powder obtained in the step (2) into the peroxy heteropoly acid solution prepared in the step (3), controlling the temperature at 70 ℃, stirring for 20h, filtering, separating to obtain a product, washing with deionized water until the washing water is neutral, and baking in a 120 ℃ oven for 10h to obtain raw catalyst powder;
(5) and (3) mixing the catalyst raw powder obtained in the step (4) with aluminum sol, wherein the mass ratio of the catalyst raw powder to the aluminum sol is 1:1, the mass percentage concentration of the aluminum sol is 30%, stirring, granulating, and baking at 70 ℃ for 30 hours to obtain a granular catalyst finished product.
The prepared catalyst is used for oxidizing olefin such as dicyclopentadiene and the like into epoxy compounds by using hydrogen peroxide as an oxidizing agent, and the product yield is 96.6%.
Claims (5)
1. The solid acid catalyst for olefin epoxidation reaction is characterized in that inorganic nano oxide subjected to grafting modification treatment by quaternary ammonium salt is used as a carrier, and an active component is heteropoly acid or peroxy heteropoly acid, wherein the inorganic oxide is nano MgO or SiO2、Al2O3Or any combination thereof.
2. A process for preparing a solid acid catalyst for olefin epoxidation according to claim 1, comprising the steps of:
(1) weighing a certain amount of inorganic oxide powder, a silylation reagent and a solvent, putting into a reactor, mixing and stirring to react, wherein the reaction temperature is in the range of 30-120 ℃, and the reaction time is in the range of 8-30 hours;
wherein: the inorganic oxide powder is nano MgO or SiO2、Al2O3The silylation reagent is a silylation reagent containing quaternary ammonium salt groups, and the silylation reagent has any one of the following two chemical formulas:
RmSi(OR)3-m(CH2)nN+R1R2R3X-(1)
RmSiX3-m(CH2)nN+R1R2R3X-(2)
wherein N, O, Si in chemical formulas (1) and (2) respectively represent nitrogen, oxygen and silicon elements; x represents halogen, and any one of F, Cl, Br and I elements is selected; m represents the number of alkyl groups bonded to the silicon atom, and is an integer of 0 to 2; n represents the number of methylene groups connected between silicon and phosphorus atoms, and is an integer of 1-18; r, R1、R2、R3Selected from alkyl, phenyl or benzyl with 1-18 carbon atoms;
the solvent is one or any combination of benzene, toluene, petroleum ether, acetonitrile, dichloroethane, tetrahydrofuran, 1, 2-epoxy hexacyclic ring and dichloroethane; the molar ratio of the inorganic oxide powder to the silylation agent is 25: 1-740: 1, and the mass ratio of the solvent to the inorganic oxide powder is 5: 1-2: 1;
(2) filtering the product in the step (1), separating solid powder from the solution, washing the separated solid powder with the solvent in the step (1), wherein the mass ratio of the solvent for washing to the inorganic oxide powder in the step (1) is 5: 1-2: 1, removing unreacted silylation reagent in the solid powder, and drying the solid powder;
(3) preparing a heteropoly acid solution: weighing a certain amount of heteropoly acid and dissolving the heteropoly acid in a solvent, wherein the concentration of the heteropoly acid is 0.01-0.20 g/ml, and the solvent is any one or a mixture of more of pure water, methanol, ethanol, acetone, chloromethane, tetrahydrofuran and 1, 4-dioxane; or, preparing a peroxy heteropoly acid solution: weighing a certain amount of heteropoly acid solid, slowly adding the heteropoly acid solid into hydrogen peroxide solution with the mass concentration of 30-70 percent, and mixing heteropoly acid and H2O2The mass ratio is in the range of 1:1 to 1:3, and is in the range of 20 to up toStirring for 2-5 h at the temperature of 30 ℃ to obtain a peroxy heteropoly acid solution;
wherein the molar ratio of the heteropoly acid or the peroxy heteropoly acid to the silylation reagent is 1: 1-1: 3;
(4) adding the solid powder obtained in the step (2) into the heteropoly acid or heteropoly acid peroxide solution prepared in the step (3), controlling the temperature at 30-80 ℃, stirring for 20-30 h, filtering, separating to obtain a product, washing with deionized water until the washing water is neutral, and baking in an oven at 40-120 ℃ for 10-40 h to obtain raw catalyst powder;
(5) mixing the catalyst raw powder obtained in the step (4) with silica sol or aluminum sol, wherein the mass ratio of the catalyst raw powder to the silica sol or the aluminum sol is 4: 1-1: 1, the mass percentage concentration of the silica sol or the aluminum sol is 20-30%, stirring, granulating, and baking at 70-120 ℃ for 10-30 hours to obtain a granular catalyst finished product.
3. A process for the preparation of a supported heteropolyacid catalyst according to claim 2, characterized in that: in the step (1), X in the chemical formulas (1) and (2) is Cl; n is an integer of 1-3; r, R1、R2、R3The alkyl group having 1 to 18 carbon atoms is any one of methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, heptyl, octyl, dodecyl, tetradecyl, hexadecyl, and octadecyl.
4. Use of the solid acid catalyst according to claim 1 for the epoxidation of an olefin, wherein the catalyst is used in the epoxidation of an olefin.
5. The use of the solid acid catalyst for olefin epoxidation according to claim 4, wherein the catalyst is used in a reaction for preparing dicyclopentadiene dioxide by oxidation of dicyclopentadiene.
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